Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS5594045 A
Publication typeGrant
Application numberUS 08/347,413
Publication dateJan 14, 1997
Filing dateMay 25, 1993
Priority dateJun 3, 1992
Fee statusLapsed
Also published asDE69305637D1, EP0643746A1, EP0643746B1, US5726221, WO1993024579A2, WO1993024579A3
Publication number08347413, 347413, US 5594045 A, US 5594045A, US-A-5594045, US5594045 A, US5594045A
InventorsMichael Alexiou
Original AssigneeAlexiou; Michael
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Correction fluids
US 5594045 A
Abstract
Water-based correction fluids for covering typing, writing or drawing errors contain a particulate opacifier, a water-soluble or water-dispersible binder, water and a di- or tri-quaternary ammonium compound to prevent bleed of inks.
Images(4)
Previous page
Next page
Claims(11)
I claim:
1. A water-based correction fluid, which comprises a particulate opacifier, a water-soluble or water-dispersible polymeric binder, water and a di- or tri-quaternary ammonium compound of the formula: ##STR3## where R1 and R2, which may be the same or different, are substituted or unsubstituted aliphatic groups containing from 4 to 20 carbon atoms, R3 and R4, which may be the same or different, are substituted or unsubstituted alkylene groups containing up to 8 carbon atoms, which groups may be interrupted by one or more ethereal oxygen atoms, wherein A is an anion, and n is 0 or 1.
2. A correction fluid according to claim 1, in which, in the compound R1 and R2 are both --C8 H17, --C10 H21, --C12 H25, --C14 H29, or --C18 H37 ; R3 and R4 are both --C2 H4 -- or --C3 H6 --, and A-- is a chloride or bromide anion.
3. A correction fluid according to claim 1, which comprises, by weight, from 40 to 70% of opacifier, from 1 to 10 % of polymeric binder, from 25 to 30% of water, and from 1 to 10% of di- or tri-quaternary ammonium compound.
4. A correction fluid according to claim 1 in which the opacifier is titanium dioxide.
5. A correction fluid according to claim 1 which additionally comprises up to 30% by weight of an inert filler.
6. A correction fluid according to claim 5, in which the inert filler is powdered calcium carbonate or hollow microspheres of hydrated alumina, alumina-silica alloy, or acrylate-styrene copolymer.
7. A correction fluid according to claim 1 further including zinc oxide and zinc acetate.
8. A correction fluid according to claim 1 wherein the polymeric binder is polyvinyl alcohol or a water-dispersible or -soluble acrylic polymer or polyurethane.
9. A correction fiuid according to claim 8 which comprises from 1 to 5% by weight of the polymeric binder.
10. A correction fluid according to claim I which additionally comprises from 1 to 5% by weight of a dispersing agent which is compatible with the cationic materials present.
11. A correction fluid according to claim 1 which additionally comprises up to 10% by weight of a cationically modified clay and/or powdered polyacrylonitrile.
Description

This invention is concerned with correction fluids, that is white paints which are used by typists and others to cover typing, writing and drawing errors and which, when dry, can be typed, written or drawn over.

Correction fluids essentially comprise an opacifying agent, usually a white pigment, such as titanium dioxide, a polymeric binder, and a liquid medium in which the binder is soluble or dispersible. The composition usually also contains a dispersing agent. Such compositions are of two kinds. In the first kind the liquid medium is a volatile organic solvent, such as a chlorohydrocarbon, a chlorofluorocarbon or a petroleum-based hydrocarbon, and in the second kind the liquid medium is water-based, for example a water/ethanol mixture.

There is a general movement and, in some countries, a positive requirement, to avoid the use of organic solvent-containing compositions for environmental reasons and/or to reduce the incidence of solvent abuse. The present invention is concerned with correction fluids of the second kind, that is containing water as the liquid medium.

The water-based correction fluids that are currently available are entirely satisfactory with typewriter and printer inks since these are based on waxes and greases, that is they are non-aqueous. Water-based correction fluids are not generally satisfactory with ball point pen inks even though the latter are based on greases since certain of the dyes used in such inks have a residual water-solubility. Such correction fluids are also unsatisfactory with markings made with water-based inks.

When water-based correction fluids are used on markings made with water-based inks or with ball point pens, it is found that although the coating of the correction fluid initially appears to cover and obscure the markings, the latter show through before or after the coating is completely dry. This phenomenon is referred to as "bleeding" and is due to the water in the correction fluid solubilising the dye or dyes present in the ink of the marking.

A variety of dyes are used in water-based inks and ball point pen inks and the problem of bleeding appears to be particularly bad with inks containing anionic dyes.

There have been various proposals for dealing with the problem of "bleeding" in water-based correction fluids. In one proposal, described in WO 92/07039, there is used as the polymeric binder of the correction fluid a cationically effective film-forming material, especially an acrylate polymer, to bind with the anionic dye to prevent "bleeding" However, there are few suitable such film-forming materials and their use limits considerably the possible variations in formulation of the fluids which are generally desirable. Another proposal, described in Research Disclosure, May 1979, item 18182 (anonymous), also suggests the use in a correction fluid of a cationic material to bind with the anionic dye, but in this case the cationic material is contributed by polymeric or other water-soluble materials such as quaternary ammonium surfactants. The only example given is the use of a cationic polymeric compound SOLIDIGEN LT-13, described as a proprietary material supplied by General Aniline and Film Corp.

We have now found that there is a particular narrow group of quaternary ammonium compounds which are especially satisfactory in water-based correction fluids for preventing "bleeding". These compounds are capable of reacting rapidly with and insolubilising the anionic dyes used in such inks, whilst not significantly limiting the choice of other components of the compositions.

According to one aspect of the present invention, therefore, there is provided a water-based correction fluid, which comprises a particulate opacifier, a water-soluble or water-dispersible polymeric binder, water and a di- or tri-quaternary ammonium compound of the formula: ##STR1## where R1 and R2, which may be the same or different, are substituted or unsubstituted aliphatic groups containing from 4 to 20 carbon atoms, R3 and R4, which may be the same or different, are substituted or unsubstituted alkylene groups containing up to 8 carbon atoms, which groups may be interrupted by one or more ethereal oxygen atoms, A is an anion, and n is 0 or 1.

The compounds of formula I are either known or are close analogues of known compounds, although we are not aware of any prior proposal to use these compounds for the purpose with which the invention is concerned. These compounds can be prepared by methods which have been published in the literature or by adaptations of such methods which will be apparent to those skilled in the art.

Preferred compounds of formula I for use in accordance with the invention are compounds in which R1 and R2 are both --C8 H17, --C10 H21, --C12 H25, --C14 H29, or --C18 H37, R3 and R4 are both --C2 H4 -- or --C3 H6 --, and A-- is a chloride or R3 and R4 are both --C2 H4 -- or --C3 H6 --, and A-- is a chloride or bromide anion. The groups R1, R2, R3 and R4 can each independently be substituted such as by one or more hydroxyl groups or halogen atoms, for example.

It is usually preferred to use diquaternary ammonium compounds (I, n=0), rather than triquaternary ammonium compounds (I, n=1).

Specific diquaternary compounds which have been prepared and used and which are effective for the purpose indicated, are as follows (in these compounds, R1 =R2 ; R3 =--C2 H4 --; and n=0):

______________________________________               R1 /R2                      m.p.______________________________________N,N'-dioctyl-N,N,N',N'-                 C8 H17                          .sup. 150 C..sup.tetramethylethylenediamine dibromideN,N'-didecyl-N,N,N',N'-                 C10 H21                          153 C.tetramethylethylenediamine dibromideN,N'-didodecyl-N,N,N',N'-                 C12 H25                          168 C.tetramethylethylenediamine dibromideN,N'-ditetradecyl-N,N,N',N'-                 C14 H29                          168 C.tetramethylethylenediamine dibromideN,N'-dioctadecyl-N,N,N',N'-                 C18 H37                          170 C.tetramethylethylenediamine dibromide                          (decomp)______________________________________

Whilst the above terminology is used in the present specification, it will be clear to those skilled in the art that alternative terminology can be used: for example, the ditetradecyl compound can be named 1,2-ethanediaminium-N,N-dietetradecyl-N,N,N',N'-tetramethyl dibromide.

An example of a useful ether is N,N'-didecyl-N,N,N',N'-tetramethyl-1,5 (3-oxapentylene) diammonium dichloride. An example of a useful triquaternary compound is N,N',N"-trioctyl-N,N,N',N',N"-pentamethyldiethylenetriamine tribromide.

The diquaternary ammonium compounds of formula I (n=0) in which R1 and R2 are the same may be prepared by condensing an excess of an alkyl halide of the formula R1 X, where X is a halogen atom, with an N,N'-tetramethylalkylenediamine of the formula: ##STR2## where R3 has the above-stated meaning- Since two moles of the alkyl halide are required per mole of the tetramethylalkylenediamine, the excess should be in excess of two moles. This reaction will give rise to a diquaternary ammonium compound of formula I in which A-- is the halide ion, X--. Preferred compounds of formula I are those in which A-- is a chloride or bromide ion. Compounds containing other anions, that is other than halides, can be made by treating the product of the condensation reaction with an excess of a salt containing the desired anion.

The condensation reaction is preferably carried out by simply heating a mixture of the two reactants where one or both of them is a liquid. Where neither is a liquid either at room temperature or at the elevated temperature used for the reaction, an inert organic solvent, for example toluene, is preferably used as the reaction medium.

Suitable temperatures for the condenstation reaction are, for example, from 80 to 90 C. and the reaction time is typically about 16 hours.

The product usually precipitates out of the liquid reaction mixture and, where no organic solvent is used, the reaction mixture becomes a solid mass. The desired product is obtained by recrystallisation, for example from methyl ethyl ketone, or by any other suitable procedure.

As already indicated, we have found that the di- and tri-quaternary ammonium compounds of formula I are capable of effectively insolubilising the anionic dyes used in water-based inks. The correction fluids in which they are used preferably comprise, by weight:

______________________________________opacifier         40-70%polymeric binder  1-10%water             25-30%di- or tri-quaternary             1-10%ammonium compounddispersing agent  0.1-5%______________________________________

The nature and preferred examples of these components and of other optional components will now be further described.

The opacifier may be any of those conventionally used in correction fluids. Titanium dioxide pigment is preferred, for example the grades Ti Pure R900 and Ti Pure R700 supplied by du Pont and the grade RCL-535 supplied by SCM Chemicals.

In addition to the opacifier, the correction fluid may, and preferably does, contain an inert filler which has some covering power, but is less expensive than titanium dioxide. Suitable fillers for this purpose include, for example, calcium carbonate and hollow microspheres of hydrated alumina (commercially available under the Trade Mark "Spacerite"), of alumina-silica alloy (commercially available under the Trade Mark "Zeospheres"), and of acrylate-styrene copolymer (commercially available under the Trade Mark "Ropaque OP-62"). The composition may contain up to 30% by weight of one or more of such fillers and preferably contains from 10 to 20% by weight.

It can be advantageous to include zinc salts in the correction fluids of the invention. A preferred combination is zinc oxide with a small amount of zinc acetate activator. The zinc compounds form a cement in the correction fluid as it dries. Typical amounts of zinc compounds would be about 20% zinc oxide and about 0.5% zinc acetate.

The polymeric binder should, as previously indicated, be water-soluble or water-dispersible and it should not interact with the cationic materials present in the composition. A preferred polymeric binder is polyvinyl alcohol: material which is 80% hydrolysed and which has a molecular weight of about 125000 is particularly preferred.

Aqueous dispersions and solutions of acrylic polymers stabilised by non-ionic or cationic surfactants are also suitable, for example "Plextol B500" and "Plex 4739L" (Trade Marks) supplied by Rohm.

Aqueous dispersions of polyurethanes stabilised by cationic surfactants are also suitable, for example YA-110-5 supplied by witco Corp.

Aqueous dispersions of polyvinyl acetate (usually copolymerised with minor amounts of dimethylamino ethyl methacrylate) can be used.

It is particularly preferred to use up to 5% by weight of the polymeric binder.

As indicated, the correction fluid according to the invention preferably comprises from 1 to 5% of a dispersing agent. This component is preferably present not only to maintain the opacifier in suspension, but also to reduce the viscosity of the fluid so that it is of a readily paintable consistency. The dispersing agent used should be one which is compatible with the cationic materials present.

Preferred dispersing agents are cocoamine acetate such as that available under the Trade Mark "Armac C" from Akzo Chemie and acrylic graft copolymers such as that available under the Trade Mark "Hypermer CG-6" from ICI.

Water-based inks may also contain cationic dyes and ball point pen inks may contain solvent dyes which have a residual water solubility such as to cause bleed through. In order to insolubilise these two types of dye, the correction fluid preferably contains a cationically modified clay and/or powdered polyacrylonitrile, both of which physically adsorb and thus insolubilise cationic dyes. A suitable cationically modified clay is, for example, the SD 903 material (known as Macrosorb AX 300) available from Crosfield Chemicals and a suitable polyacrylonitrile powder is available from Aldrich Chemical Co.

The proportion of such an adsorbent present in the correction fluid is preferably up to 10% by weight, more preferably from 4 to 7% by weight.

In order that the invention may be more fully understood, the following examples, in which all the percentages are by weight, are given by way of illustration only:

EXAMPLE 1

A correction fluid of the following composition was made up:

______________________________________                 %______________________________________titanium dioxide        56.31(Ti-Pure R900)polyvinyl alcohol       0.97(80% hydrolysed; MW 125000)water                   39.81N,N'-ditetradecyl-N,N,N',N'-                   2.91tetramethylethylenediamine dibromide______________________________________

The correction fluid was applied by a brush in the conventional way to markings on paper which had been made with a water-based ink containing anionic dyes, so as to cover the markings. The correction fluid dried in approximately 60 seconds to form an opaque white film on the paper completely hiding the markings. There was no bleed through.

The white film could be written on as soon as it was dry.

EXAMPLE 2

Correction fluids were made up of the composition described in Example 1 except that the N,N'-ditetradecyl-N,N,N',N'-tetramethylethylenediamine dibromide was replaced by, respectively, the corresponding dioctyl, didecyl, didocyl and dioctadecyl compounds. Also, a composition was made containing N,N'-methylene bis (dimethyltetradecylammonium bromide). When tested as described in Example 1, the fluids showed antibleed activity and the white films produced could be written on as soon as they were dry.

EXAMPLE 3

A correction fluid of the following composition was made up:

______________________________________                 %______________________________________titanium dioxide        60.31(Ti-Pure R900)acrylic polymer binder  12.90(Plex 4739L solution)water                   15.25N,N'-didodecyl-N,N,N',N'-                   3.24tetramethylethylenediamine dibromideacrylic graft copolymer 8.30dispersant (Hypermer CG-6)______________________________________

The correction fluid was used in the same way as in Example 1 to cover markings on paper which had been made with a water-based ink containing anionic dyes. Similar results were obtained; there was no bleed through.

EXAMPLE 4

A correction fluid of the following composition was made up:

______________________________________                 %______________________________________titanium dioxide        28.7(Ti-Pure R900)zinc oxide b.p.         19.1zinc acetate            0.5water                   22.0quaternary ammonium compound                   10.3Hypermer CG-6           10.5Vinamul V90061          8.8Foamaster 8034          0.1______________________________________

The quaternary ammonium compound was N,N',N"-trioctyi-N,N,N',N',N"-pentamethyldiethylenetriamine tribromide. When tested as in Example 1, the fluid formed an opaque white coating with non-bleed activity.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2084918 *Nov 5, 1936Jun 22, 1937Nat Lead CoAlcoholic suspension of titanium pigments
US3356627 *Jun 17, 1963Dec 5, 1967Rohm & HaasAqueous blends of two water-insoluble polymers, one of which has 1 to 15% of a monomer containing an alcoholic hydroxyl, amino, amido or ureido group
US3637565 *Nov 30, 1964Jan 25, 1972Dow Chemical CoLatex compositions having improved adhesion
US3674729 *Jul 7, 1970Jul 4, 1972Battelle Development CorpCorrection fluid composition
US3847857 *Nov 5, 1973Nov 12, 1974Rohm & HaasStain resistant coating composition
US3875105 *Jan 23, 1973Apr 1, 1975Scripto IncErasable writing medium suitable for use in ball point pens
US3926890 *Dec 4, 1972Dec 16, 1975Mitsubhishi Gas Chemical CompaProcess for producing cationic synthetic latex involving emulsion polymerization of haloalkyl esters of acrylic and methacrylic acid followed by quarternization with tertiary amine
US3985663 *Mar 14, 1974Oct 12, 1976Xerox CorporationConductive inks containing quaternary ammonium compounds
US3997498 *Jul 24, 1975Dec 14, 1976Xerox CorporationHalogenated ethane, pigment, binder
US4043820 *Jun 10, 1975Aug 23, 1977Ozalid Group Holdings, LimitedFor diazotype copying materials
US4165988 *Dec 27, 1977Aug 28, 1979Columbia Ribbon And Carbon Manufacturing Co., Inc.Methyl chloroform, perchloroethylene, pigment, film-forming binder material
US4228028 *Nov 13, 1978Oct 14, 1980Burroughs CorporationBall point pen, ink, and its eradicator system
US4248754 *Dec 5, 1978Feb 3, 1981Dulux Australia LtdWaterproof paints
US4290072 *Jan 28, 1980Sep 15, 1981American Can CompanyPolymers, coating
US4308186 *Jul 7, 1980Dec 29, 1981North American Philips CorporationTitanium dioxide film
US4352901 *Aug 14, 1980Oct 5, 1982American Can CompanyOpaque jet ink compositions
US4399254 *Sep 25, 1981Aug 16, 1983Ppg Industries, Inc.Surfactant with methanesulfonic acid anion
US4507422 *May 21, 1984Mar 26, 1985Allied Colloids LimitedWater soluble polymers and dispersions containing them
US4554307 *Nov 16, 1984Nov 19, 1985Allied Colloids LimitedContaining acid groups
US4654081 *Jul 2, 1984Mar 31, 1987Minnesota Mining And Manufacturing CompanyThermoplastic resin, pigment, fluorinated solvent
US4655834 *Aug 1, 1985Apr 7, 1987Canon Kabushiki KaishaNontoxic; storage stable
US4695528 *Sep 28, 1982Sep 22, 1987Wolfgang DabischProcess for forming images using body with reversible fixable and temperature-variable light extinctions
US4732614 *Jul 15, 1985Mar 22, 1988The Gillette CompanyPressure sensitive chemical recording
US4740549 *Jul 10, 1986Apr 26, 1988Toyo Soda Manufacturing Co., Ltd.Ink composition for writing board
US5256191 *Oct 1, 1991Oct 26, 1993John ThompsonOpacifying pigment dispersed in solution of film forming polymer and volatile organosiloxane in volatile solvent
US5332599 *Jul 19, 1993Jul 26, 1994The Gillette CompanyLatex binders with opacifying pigments, protective colloids, surfactants and water
US5338775 *May 19, 1992Aug 16, 1994The Gillette CompanyCorrection fluid
DD254586A1 * Title not available
DE3919588A1 *Jun 15, 1989Dec 21, 1989Kores Holding Zug AgWater-based universal correction fluid
JPH0297570A * Title not available
JPH0297574A * Title not available
JPH0331375A * Title not available
JPH01254962A * Title not available
JPH01292074A * Title not available
JPH02129274A * Title not available
JPH02169678A * Title not available
JPH02202561A * Title not available
JPH02209973A * Title not available
JPH02263876A * Title not available
JPS5849761A * Title not available
JPS6068996A * Title not available
JPS58162674A * Title not available
JPS59131675A * Title not available
JPS60250990A * Title not available
JPS61174274A * Title not available
SU891730A1 * Title not available
WO1992007039A1 *Sep 2, 1991Apr 30, 1992Tipp Ex Gmbh & Co KgCorrector fluid with aqueous suspension medium capable of preventing bleeding of the ink
Non-Patent Citations
Reference
1"Correction Fluid For Dye Based Ink Print", Abstract, 18182, Research Disclosure, (May 1979).
2Alince, "Performance of cationic latex as a wet-end additive", Tappivol. 60 12:133-136 (Dec. 1977).
3 *Alince, Performance of cationic latex as a wet end additive, Tappi vol. 60 12:133-136 (Dec. 1977).
4 *Correction Fluid For Dye Based Ink Print, Abstract, 18182, Research Disclosure, (May 1979).
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5958121 *Mar 24, 1998Sep 28, 1999Xerox CorporationSet of inks comprising first aqueous ink consisting of anionic colorant, second aqueous ink containing ammonium salt, wherein first colorant is immobilized on substrate by interaction with ammonium salt, reducing intercolor bleed
US6083618 *Jun 25, 1997Jul 4, 2000The Gillette CompanyCorrection fluids comprising composite polymeric particles
Classifications
U.S. Classification523/161, 524/497, 524/557, 524/432, 524/444, 524/236, 106/31.75, 524/425, 524/556, 524/503
International ClassificationB43L19/00, C09D10/00
Cooperative ClassificationC09D10/00
European ClassificationC09D10/00
Legal Events
DateCodeEventDescription
Mar 3, 2009FPExpired due to failure to pay maintenance fee
Effective date: 20090114
Jan 14, 2009LAPSLapse for failure to pay maintenance fees
Jul 21, 2008REMIMaintenance fee reminder mailed
Jan 28, 2004FPAYFee payment
Year of fee payment: 8
Jul 13, 2000FPAYFee payment
Year of fee payment: 4